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Aqueous Photocurrent Measurements Correlated to Ultrafast Electron Transfer Dynamics at Ruthenium Tris Diimine Sensitized NiO Photocathodes Nicolas Queyriaux,†,# Ruri A. Wahyuono,‡,§,# Jennifer Fize,† Corinne Gablin,∥ Maria Wac̈ htler,‡,§ Eugénie Martinez,⊥ Didier Léonard,*,∥ Benjamin Dietzek,*,‡,§ Vincent Artero,† and Murielle Chavarot-Kerlidou*,† †

Laboratoire de Chimie et Biologie des Métaux, UMR 5249 Université Grenoble Alpes, CNRS, CEA, 17 rue des Martyrs, 38000 Grenoble, France ‡ Leibniz Institute of Photonic Technology (IPHT) Jena e. V., Albert-Einstein-Strasse 9, Jena 07745, Germany § Institute for Physical Chemistry and Center for Energy and Environmental Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, Jena 07743, Germany ∥ Université de Lyon, CNRS, Université Claude Bernard Lyon 1, ENS de Lyon, Institut des Sciences Analytiques, UMR 5280, 5 rue de la Doua, 69100 Villeurbanne, France ⊥ CEA, Leti, MINATEC Campus, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France S Supporting Information *

ABSTRACT: Understanding the structural and electronic factors governing the efficiency of dye-sensitized NiO photocathodes is essential to optimizing solar fuel production in photoelectrochemical cells (PECs). For this purpose, three different ruthenium dyes, bearing either two or four methylphosphonate anchoring groups and either a bipyridine or a dipyridophenazine (dppz) ancillary ligand, were synthesized and grafted onto NiO films. These photoelectrodes were fully characterized by XPS, ToFSIMS, and UV−vis absorption, time-resolved emission, and femtosecond transient absorption spectroscopies. Increasing the number of anchoring groups from two to four proved beneficial for the grafting efficiency. No significant modification of the electronic properties compared to the parent photosensitizer was observed, in accordance with the nonconjugated nature of the grafted linker. The photoelectrochemical activity of the dye-sensitized NiO electrodes was assessed in fully aqueous medium in the presence of an irreversible electron acceptor, and photocurrents reaching 190 μA·cm−2 were recorded. The transient absorption study revealed the presence of two charge recombination pathways for each of the sensitizers and evidenced a stabilized charge separated state in the dppz derivative, supporting its superior photoelectrochemical activity.

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INTRODUCTION In the context of global energy demand, the construction of tandem dye-sensitized photoelectrochemical cells (DS-PECs) for solar hydrogen production or carbon dioxide reduction is promising, yet challenging.1−6 Their design is based on the assembly of two photoelectrodes, a photoanode driving the oxidation of water into oxygen in order to supply the photocathode with protons and electrons to achieve proton and/or CO2 reduction. In this approach, an efficient grafting of molecular photosensitizers and/or (photo)catalysts onto a © XXXX American Chemical Society

suitable metal oxide electrode is mandatory. The strategy behind the success of the dye-sensitized solar cells,7,8 pioneered by Grätzel, based on the covalent grafting of carboxylate-9 or phosphonate-substituted10 dyes onto a suitable semiconducting metal oxide, was applied first to the construction of various dyesensitized photoanodes.11−26 On the other hand, dye-sensitized Received: December 13, 2016 Revised: February 13, 2017 Published: February 20, 2017 A

DOI: 10.1021/acs.jpcc.6b12536 J. Phys. Chem. C XXXX, XXX, XXX−XXX

The Journal of Physical Chemistry C

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photocathodes for H2 production6,27−33 or CO2 reduction34,35 emerged more recently. They all rely on nickel oxide (NiO), which is a low-cost and easy-to-process p-type semiconductor, suitable for hole injection into its valence band.5 Various nanostructured NiO film preparations have been reported over the years and recently evaluated with respect to their performance as photocathodes in a comprehensive benchmarking study.36 Ruthenium tris diimine complexes were often employed as sensitizers for NiO29,30,32,35 and combined to suitable catalysts according to three different architectures of dye-sensitized H2-evolving photocathodes: grafting of a covalent photocatalyst,29,35 cografting of photosensitizer and catalyst,30 or layer-by-layer assembly of the latter.32 One important drawback limiting the efficiency of NiO-based photocathodes is the fast recombination occurring, after the initial hole injection, between the hole in the semiconductor and the reduced photosensitizer.37 Structural optimizations of the latter were thus reported in order to slow down this process, detrimental for photoelectrochemical activity. As far as ruthenium photosensitizers are concerned,38−46 the group of F. Odobel first established that the insertion of a nonconjugated spacer, methylene group typically, between the anchoring function and the complex could favorably decrease the electronic coupling with NiO.38,39 In a related approach, Wu and co-workers increased the length of the conjugated spacer between the semiconductor surface and a cyclometalated ruthenium photosensitizer.40 Elegant molecular engineering, based on the dyad concept, was also independently developed by the groups of L. Hammarström and Y. Wu, to delocalize the charge on the reduced dye away from the surface.41−43 While complex architectures with optimized push−pull character have been proposed, Bräutigam and colleagues alternatively showed that asymmetric substitution of the paradigmatic Ru(bpy)3 core is already sufficient to induce an asymmetric metal-to-ligand charge transfer in the photosensitizer, which in turn influences the hole injection process characteristics.44 These Ru-sensitized photocathodes, nevertheless, exhibit a large discrepancy in their recombination kinetics, ranging from a few hundred picoseconds40,43,44 to microseconds.41 This suggests that some recombination pathways can be overlooked, as recently highlighted for an organic dye-sensitized NiO electrode.47 These results also reflect the fact that charge recombination is an intricate process, still a matter of debate as for its underlying mechanisms;48 a deeper understanding of the various parameters controlling interfacial electron transfer at dyesensitized NiO electrodes is thus required in order to optimize their efficiency for solar fuel production. Herein, we report the preparation and characterization of nanostructured NiO films sensitized by a series of phosphonate-substituted ruthenium polypyridyl complexes. Special attention was paid to the number of phosphonate anchoring groups carried by the photosensitizer (four versus two) and to the nature of the third diimine ligand. The π-accepting dipyridophenazine (dppz) ligand was selected as a model system, prefiguring charge transfer properties which could favorably remove the electron density of the reduced dye away from the NiO surface. The resulting photoelectrodes were characterized by various techniques, including surface mass spectrometry analysis (ToF-SIMS). Their photoelectrochemical activity was assessed under aqueous conditions, and the dynamics of the corresponding interfacial electron transfers was investigated by time-resolved emission and ultrafast transient absorption spectroscopies.

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EXPERIMENTAL SECTION

Synthesis and Dye-Sensitized NiO film Preparation. All reagents were purchased from Sigma-Aldrich and used as obtained unless otherwise stated. Reagent-grade solvents were used without further purification. The 4,4′-bis(diethylphosphonomethyl)-2,2′-bipyridine ligand (4,4′(CH2PO3Et2)2-bpy) was custom-synthesized by the company Azasynth, according to a previously reported procedure.49 The dipyrido[3,2-a:2′,3′-c]phenazine (dppz) ligand,50 [Ru(bpy)3](PF 6 ) 2 , 5 1 [Ru(bpy) 2 (dppz)](PF 6 ) 2 , 5 0 and [Ru(4,4′(CH2PO3Et2)2-bpy)(bpy)2](PF6)2 (RuP2OEt-bpy)49 were synthesized according to reported procedures. NiO films (two layers, screen-printed onto conductive glass) were purchased from Dyenamo AB, Stockholm, Sweden. 1H and 13C NMR spectra were recorded at 298 K on a Bruker Avance 300 MHz spectrometer. NMR data are referenced to the residual solvent peak and reported relative to tetramethylsilane reference (δ = 0 ppm). UV−vis absorption spectra were recorded either on a Shimadzu UV-1800 spectrometer (complexes in solution) or on an Agilent Cary 60 UV−vis spectrometer equipped with a solid sample holder. Electrospray ionization mass spectrometric (ESI-MS) measurements were carried out on a Thermoquest Finnigan LCQ spectrometer. General Procedure for the Synthesis of [Ru(4,4′(CH2PO3Et2)2-bpy)2(N∧N)](PF6)2 (N∧N: bpy or dppz). A solution of commercially available Ru(dmso)4Cl2 (420 mg, 0.88 mmol) and 4,4′-(CH2PO3Et2)2-bpy (800 mg, 1.75 mmol) in methanol (100 mL) was refluxed overnight under argon. Removal of the solvent and drying under vacuum yielded the dark-red highly hygroscopic intermediate [Ru(4,4′(CH2PO3Et2)2-bpy)2Clx(dmso)2−x]Cl2−x. This intermediate was not purified and could be stored in the dark under argon for weeks. A solution of [Ru(4,4′-(CH 2 PO 3 Et 2 ) 2 bpy)2Clx(dmso)2−x]Cl2−x (1 equiv, using an average molecular weight) and N∧N (1 equiv) in a water/ethanol (1:3) mixture was refluxed overnight. After cooling to room temperature, 5 mL of a saturated KPF6 aqueous solution was added to the reaction mixture. Extraction with dichloromethane and removal of the organic solvent yield a crude reddish solid. After purification by flash chromatography on silica gel (MeCN/ aqueous KNO3 (0.4 M), 80:20) followed by anion metathesis, [Ru(4,4′-(CH2PO3Et2)2-bpy)2(N∧N)](PF6)2 (RuP4OEt-bpy and RuP4OEt-dppz) were isolated as red powders. RuP4OEt-bpy (60%). 1H NMR (300 MHz, CD3CN) δ (ppm) 8.46 (d, J = 8.1 Hz, 2H), 8.37 (s, 4H), 8.01 (t, J = 7.8 Hz, 2H), 7.66 (d, J = 5.0 Hz, 2H), 7.60 (d, J = 5.4 Hz, 4H), 7.43−7.33 (m, 2H), 7.30 (s, 4H), 4.15−3.80 (m, 16H), 3.35 (d, JPH = 22.5 Hz, 8H), 1.32−0.95 (m, 24H).13C NMR (75 MHz, CD3CN): δ (ppm) Cq: 158.0, 157.5, 151.5, 151.4, 151.2, 146.1, 146.0, 145.96, 145.9, 137.8, 128.7, 128.6, 127.5, 126.2, 125.3, 124.3, 62.5, 62.4, 33.5, 31.7, 16.6, 15.7. ESI-MS: m/z 585.3 [M − 2PF6]2+. HRMS (ESI): calcd for C50H68N6O12P4Ru ([M − 2PF6]2+): m/z 585.143910; found: 585.144699. RuP4OEt-dppz (55%). 1H NMR (300 MHz,CD3CN) δ (ppm) 9.67 (d, J = 8.2 Hz, 2H), 8.47 (s, 4H), 8.43 (s, 2H), 8.20−8.10 (m, 4H), 7.90 (dd, J = 8.2, 5.4 Hz, 2H), 7.76 (d, J = 5.8 Hz, 2H), 7.63 (d, J = 5.9 Hz, 2H), 7.42 (d, J = 5.8 Hz, 2H), 7.20 (d, J = 5.8 Hz, 2H), 4.00 (d, J = 29.8 Hz, 16H), 3.39 (dd, J = 27.1, 22.6 Hz, 8H), 1.26−1.01 (m, 24H). 13 C NMR (75 MHz,CD3CN): δ (ppm) 157.8, 157.5, 154.6, 152.8, 152.4, 151.5, 146.2, 143.8, 141.0, 134.4, 133.5, 132.0, 130.7, 129.6, 128.4, 126.2, 63.5, 34.5, 32.7, 16.7. ESI-MS: m/z 648.1 [M − B


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Figure 1. Structures of ruthenium polypyridyl complexes [RuII(4,4′-(CH2PO3Et2)2-bpy)(bpy)2](PF6)2 (RuP2OEt-bpy), [RuII(4,4′-(CH2PO3Et2)2bpy)2(bpy)](PF6)2 (RuP4OEt-bpy), and [RuII(4,4′-(CH2PO3Et2)2-bpy)2(dppz)](PF6)2 (RuP4OEt-dppz) employed in this study.

water-filled liquid filter (Spectra-Physics 6123NS) and a cutoff UV filter (Spectra-Physics 59472, λ> 400 nm), respectively. Irradiance at the dye-sensitized NiO electrode was measured with a power meter (Newport PM1918-R) and adjusted to 50 mW·cm−2 (≈1 sun) using a 60% optical density filter. X-ray Photoelectron Spectrometry (XPS). The analyses were performed with a VersaProbe II spectrometer from Physical Electronics using a high-resolution monochromatic Al Kα line X-ray source at 1486.7 eV. A fixed analyzer pass energy of 23 eV was used for core level scans leading to an overall energy resolution of 0.6 eV. Survey spectra were captured at a pass energy of 117 eV. The photoelectron takeoff angle was 45°, which provided an integrated sampling depth of approximately 5 nm. All spectra were referenced against an internal signal, typically by adjusting the C 1s level peak at a binding energy of 284.8 eV. Surface Mass Spectrometry Analysis (ToF-SIMS). Time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements were carried out on a TRIFT III ToF-SIMS instrument from Physical Electronics operated with a pulsed 22 keV Au+ ion gun (ion current of 2 nA) rastered over a 300 μm × 300 μm area. An electron gun was operated in pulsed mode at low electron energy for charge compensation. The ion dose was kept below the static conditions limit. Data were analyzed using the WinCadence software. Mass calibration was performed on hydrocarbon secondary ions. Time-Resolved Fluorescence Measurements. The setup for emission lifetime measurements of ruthenium complexes both in solution and grafted onto NiO film has been described previously.53 A Hamamatsu HPDTA streak camera in concert with a Ti:sapphire laser (Tsunami, Newport Spectra-Physics GmbH) was used. To record emission, the repetition rate of the laser was reduced to 400 kHz using a pulse selector (Model 3980, Newport Spectra-Physics GmbH) and the fundamental output of the oscillator was frequency doubled to yield 390 nm pump pulses. For dye-sensitized NiO films, the sample was placed in a ca. 60° angle with respect to the excitation beam and emission light is collected from the front side of the sample in a 90° geometry. The emission spectra of ruthenium complexes both in solution and grafted onto NiO films were recorded at wavelengths between 580 and 720 nm. Femtosecond Transient Absorption Measurements. The setup for transient absorption measurement of ruthenium complex both in solution and grafted onto NiO films has been described previously.54−56 Pump pulses to excite the sample were centered at 480 nm and the pump−pulse energy was adjusted to 1.2 μJ, while typical probe intensities fall in the

2PF6]2+. HRMS (ESI): calcd for C58H70N8O12P4Ru ([M − 2PF6]2+): m/z 648.154809; found: 648.155499. Hydrolysis of Phosphoester Groups. Hydrolysis of the phosphoester groups in RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz was performed as previously reported for [Ru(4,4′-(CH2PO3H2)2-bpy)(bpy)2]Cl2.49 Preparation and Sensitization of Pristine NiO Films. The screen-printed two layer NiO plates were annealed at 450 °C for 30 min applying the following temperature protocol: from room temperature to 450 °C in 30 min; 450 °C for 30 min; gentle return to room temperature.36 The resulting NiO electrodes were soaked in methanolic solutions (10−4 M) of RuP2OH-bpy, RuP4OH-bpy, or RuP4OH-dppz for 24 h on an orbital stirring table. The electrodes were then sequentially rinsed with methanol and acetone to remove the physisorbed dyes, before being dried in a stream of argon. Electrochemical Measurements. Electrochemical analysis was performed using a BioLogic SP300 potentiostat controlled via EC-Lab V10 software. Cyclic voltammetry experiments were recorded in a classical single-compartment three-electrode cell combining a glassy carbon or a platinum working electrode, a platinum wire counter electrode, and a custom-made Ag/AgCl reference electrode (separated from the solution by a Vycor frit). Typical measurements were carried out at room temperature using 3 mL of argon-purged acetonitrile solution (0.1 M n-Bu4NBF4 as supporting electrolyte) of 1 mM complex. Measurements were corrected for ohmic drop. Ferrocene was finally added at the end of each measurement as an internal reference, allowing every measured value to be referenced versus the Fc+/Fc redox couple. Photocurrent measurements were carried out in a custom-made singlecompartment cell,52 using a typical three-electrode configuration combining the dye-sensitized NiO film as working electrode, a platinum wire counter electrode, and a custommade Ag/AgCl reference electrode (separated from the solution by a Vycor frit). Before each experiment, the Ag/ AgCl reference electrode was externally calibrated using K3[Fe(CN)6] in potassium phosphate buffer (0.1 M, pH 7). The surface of the working electrode in contact with the electrolyte was 0.50 cm2. Sodium acetate buffer (0.1 M, pH 4.5; prepared by acidification with HCl of a 0.1 M sodium acetate aqueous solution) and potassium phosphate buffer (0.1 M, pH 7; prepared by acidification with HCl of a 0.1 M K2HPO4 aqueous solution) were used as aqueous electrolytes and [CoIII(NH3)5Cl]Cl2 (20 mM) was used as an irreversible electron acceptor in solution. The electrochemical cell was back-illuminated with a 300 W xenon lamp (Oriel, ozone free). Elimination of IR and UV radiations were performed by a C


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Table 1. Photophysicala and Redox Propertiesb of Complexes RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz together with [Ru(bpy)3](PF6)2 and [Ru(bpy)2(dppz)](PF6)2 as Reference Complexes dye OEt

RuP2 -bpy RuP4OEt-bpy RuP4OEt-dppz [Ru(bpy)3](PF6)2 [Ru(bpy)2(dppz)] (PF6)2

λabs (ε)c 288 (85368), 453 (14918) 289 (91810), 457 (14665) 283 (97800), 358 (16590), 457 (16455) 286 (85030), 451 (14500) 283 (98036) 358 (17894), 450 (16681)

λem (ΦPL)d

τe

E0−0f

Eox

Ered1

Ered2

Ered3

Ered4

ΔGinjg

ΔGregh

625 (2.9) 625 (2.0) 646 (4.1)

174 197 192

2.12 2.12 2.13

+0.87 +0.87 +0.89

− − −1.35

−1.73 −1.70 −1.72

−1.93 −1.89 −1.92

−2.16 −2.15 −2.33

−0.51 −0.54 −0.53

−1.05 −1.02 −0.67

627 633

− −

2.12 2.13

+0.89 +0.91

− −1.35

−1.73 −1.79

−1.92 −2.01

−2.17 −2.31

− −

− −

a

Absorption and emission spectra were recorded in acetonitrile. bIn V vs Fc+/Fc. Cyclic voltammograms were recorded at a complex concentration of 1 mM in a 0.1 M solution of n-Bu4NBF4 in degassed acetonitrile and at a scan rate of 100 mV·s−1. cλabs in nm; ε in L·mol−1·cm−1. dλem in nm; ΦPL in %. Quantum yields were determined using fluorescein (0.1 M NaOH, ΦPL = 95%) as reference.68 eτ in ns. Emission lifetimes were measured in air-equilibrated acetonitrile. fIn eV. The 0−0 transition energy (E0−0) was considered similar to the respective parent complex, [Ru(bpy)3]2+69 and [Ru(bpy)2(dppz)]2+, respectively, assuming that the phosphonate anchoring groups do not significantly alter the chromophore properties. For [Ru(bpy)2(dppz)]2+, E0−0 was estimated from the reported maximum emission intensity at 77 K,70 with the equation E0−0 = 1240/λ. gIn eV. The Gibbs free energy for the hole injection reaction was calculated according to ΔGinj = e[EVB(NiO) − E(PS*/PS−)]; with EVB(NiO) = −0.12 V vs Fc+/071 and E(PS*/PS−) = E(PS/PS−) + E0−0. hIn eV. The Gibbs free energy for the dye regeneration by electron transfer to the irreversible electron acceptor [CoIII(NH3)5Cl]Cl2 was calculated according to ΔGreg = e[E(PS/PS−) − E(CoIII/CoII)]; the reduction potential E(CoIII/CoII) (−0.30 V vs SCE)72 was converted to Fc+/0 by subtracting 0.38 V.73

(PF6)2 and [Ru(bpy)2(dppz)](PF6)2 (Figures S1 and S2 in the Supporting Information). Spectroscopic data are summarized in Table 1. These are typical for ruthenium polypyridyl complexes, with intense absorption bands around 300 nm, attributed to ligand-centered π−π* transitions; RuP4OEt-dppz displays an additional band at 358 nm attributed to a dppz-centered transition.65 The visible part of the spectrum is dominated by the classical metal-to-ligand charge transfer (MLCT) transition centered on 450 nm. In comparison to the parent [Ru(bpy)3](PF6)2, the functionalization of bpy with weak electrondonating methyl phosphonate anchoring groups in both RuP2OEt-bpy and RuP4OEt-bpy causes a slight bathochromic shift of the MLCT bands, i.e. 0.01−0.04 eV, due to stabilization of the bpy-based π* orbital. An analogous bathochromic shift of the MLCT bands is also observable in RuP4OEt-dppz compared to [Ru(bpy)2(dppz)](PF6)2. All ruthenium complexes investigated here are weakly emissive with quantum yields of 2.9, 2.0, and 4.1% for RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz, respectively. Upon excitation at 495 nm, RuP2OEt-bpy and RuP4OEt-bpy exhibit emission with maximum intensity at 625 nm, close to that of the parent [Ru(bpy)3](PF6)2 (627 nm). Meanwhile, the emission maximum of RuP4OEt-dppz is red-shifted at 646 nm, implying that the 3MLCT emissive state is most probably localized on the dppz ligand, which is lower in energy than the bpy one. In addition, the excited states are characterized by lifetimes of 174, 197, and 192 ns for RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz, respectively (Figure S3 in the Supporting Information). Electrochemical characterization of complexes RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz (Table 1; Figure S4 in the Supporting Information) was conducted in degassed acetonitrile solution (0.1 M n-Bu4NBF4). On the anodic scan, a quasireversible one-electron wave can be identified at Eox = +0.87 for RuP2OEt-bpy, RuP4OEt-bpy, and +0.89 V vs Fc+/Fc for RuP4OEtdppz. By analogy to previous reports on related polypyridyl ruthenium complexes,49,66 this couple can be unambiguously assigned to the metal-centered RuIII/II process. On the cathodic scan, the cyclic voltammograms of complexes RuP2OEt-bpy and RuP4OEt-bpy show three quasi-reversible one-electron reductions, assigned to successive reductions of the three diimine ligands (bpy and 4,4′-(CH2PO3Et2)2-bpy). In addition,

range of 100 nJ. The mutual polarizations of pump and probe were set to the magic angle. The time resolution of the experiment was characterized by a 150 fs fwhm (full width at half-maximum) of the cross-correlation function at the fundamental 800 and 480 nm. For a kinetic analysis the differential optical density data was chirp-corrected and subsequently subjected to a global fit routine using a sum of exponentials for data analysis.57 To avoid prominent contributions from coherent artifacts,58,59 the pulse overlap region (±150 fs around time zero) was excluded in the data fitting procedure. To avoid sample degradation, the sample was moved during individual pump−probe experiments. Sample integrity was ensured by measuring the steady-state absorption spectra prior to and post each measurement.

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RESULTS AND DISCUSSION Synthesis and Characterization of the Ruthenium Photosensitizers. Phosphonic acids are well-known to form robust monolayers on transparent conducting oxides through covalent reaction with surface hydroxyl groups60−62 and to display excellent grafting stability,62 especially in the aqueous medium required for DS-PEC applications.10,49,63 Ruthenium tris diimine complexes varying either by the number of methylphosphonic acid anchoring groupstwo or fouror by the nature of the third diimine N∧N ligand (N∧N = bipyridine (bpy) or dipyridophenazine (dppz)) were selected in this study. RuP2OEt-bpy (Figure 1) was prepared by reaction of commercially available [Ru(bpy)2Cl2] with the 4,4′-bis(diethylphosphonomethyl)-2,2′-bipyridine ligand (4,4′(CH2PO3Et2)2-bpy), as previously described.49 RuP4OEt-bpy and RuP4OEt-dppz (Figure 1) were synthesized according to the following two-step procedure recently reported by Rau and coworkers:64 first, reaction of [Ru(dmso)4Cl2] with 2 equiv of 4,4′-(CH2PO3Et2)2-bpy yielded the mixture of complexes [Ru(4,4′-(CH2PO3Et2)2-bpy)2Cl2−x(dmso)x]Clx, which is not purified and directly reacted with the desired N∧N ligand to efficiently afford the [Ru(4,4′-(CH2PO3Et2)2-bpy)2(N∧N)](PF6)2 complexes. Photophysical and Electrochemical Properties. The UV/vis absorption and emission spectra of RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz were recorded in acetonitrile and compared to those of the parent compounds [Ru(bpy)3]D


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The Journal of Physical Chemistry C RuP4OEt-dppz displays an additional reductive event at −1.35 V vs Fc+/0, assigned to the pyrazine-based reduction on the dppz ligand, in comparison to the parent compound [Ru(bpy)2(dppz)](PF6)2.67 Overall, the electronic properties of the three photosensitizers are not significantly modified by the introduction of either two or four methylphosphonate substituents on the bpy ligands, in agreement with the methylene group acting as an electronic insulator between the bpy ligand and the phosphonic acid anchoring group.38 NiO Film Sensitization and Characterization. The phosphonic acid derivatives RuP2OH-bpy, RuP4OH-bpy, and RuP4OH-dppz were prepared by acidic hydrolysis of complexes RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz.74 We previously reported ITO-75 and NiO-based52 photocathodes sensitized with RuP2OH-bpy. According to these studies,52,75 film sensitization was performed by soaking the films for 24 h under orbital stirring in a 100 μM methanolic solution of the desired complex. Commercially available NiO film preparation, previously shown to display one of the highest photoelectrochemical performances in our joint benchmarking study,36 was selected here. Surface modification by the molecular ruthenium complexes was confirmed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The survey high resolution XPS spectra of the different NiO films are shown in Figure S5, together with a blank NiO film analyzed for the purpose of comparison. The chemical composition of the latter is in excellent agreement with previously reported XPS studies.76,77 These features are not modified upon sensitization with either RuP2OH-bpy, RuP4OHbpy, or RuP4OH-dppz. In addition, new peaks are observed at 132.6, 399.8, and 462.8 eV, characteristics for P 2p, N 1s, and Ru 3p3/2 core levels, respectively (Figure S6 in the Supporting Information). The highly sensitive ToF-SIMS technique was also employed to probe the films’ extreme surface in order to provide more mass-related molecular information. Spectra acquired in the positive mode exhibit numerous signatures of rutheniumcontaining ions (see Figure S7 and Table S1 in the Supporting Information), easily identified thanks to the Ru specific isotopic pattern. Two major fragmentation pathways are identified: the first one involves diimine ligand decoordination, as previously observed for Ru(bpy)3-electrografted monolayers onto glassy carbon78 (for instance, peaks detected at m/z = 414 ([Ru(bpy)2]+), 257 ([Ru(bpy-H)]+), and 157 (bpyH+) for NiO|RuP2-bpy); the second fragmentation pathway proceeds through breaking of the CH2−P bond in these phosphonatesubstituted entities (for instance, peaks detected at m/z = 438 ([Ru(bpy)(bpy(C•)(CH2•))]+) for NiO|RuP2-bpy and NiO| RuP4-bpy, at m/z = 564 ([Ru(dppz)(bpy(C•)(CH2•))]+) for NiO|RuP4-dppz). Of note, the highest intensity rutheniumcontaining secondary ions contain the nonsubstituted ligand (bpy or dppz), which enables a clear identification of each grafted dye; moreover, the phosphonate-substituted bpy ligand is never detected intact (without fragmentation), which fully supports a chemisorption rather than a physisorption process. In addition, spectra recorded in the negative mode provide further evidence for the covalent nature of the grafting of Ru complexes to NiO: various NiaPbOcHd− fragments (such as those detected at m/z = 138 (NiPO3H−), 154 (NiPO4H−), 200 (NiP2O5−), and 216 (NiP2O6−)) were identically detected for the three functionalized NiO films, compared to a blank sample (Figure S8 in the Supporting Information); this clearly

demonstrates the formation of strong P−O−Ni bonds at the surface of the NiO films, as similarly reported for phosphonic acid monolayers onto TiO2 films.79,80 Finally, ToF-SIMS allows for a chemical mapping and it was checked that high mass peaks characteristic of the grafted dyes do not exhibit any heterogeneous distribution (Figure S9 in the Supporting Information), at least at the lateral resolution obtained in the high mass resolution acquisition mode (estimated to a few micrometers). Film sensitization was further quantified by UV visible absorption spectroscopy (Figure 2 and Figure S10 in the

Figure 2. Absorption spectra of blank NiO (red line), the same film sensitized with RuP4OH-dppz (NiO|RuP4-dppz, black line), the corresponding differential spectrum (blue line) and absorption spectrum of RuP4OEt-dppz (recorded in acetonitrile; dashed green line).

Supporting Information). After subtraction of the blank NiO film absorption, the dye-sensitized electrode spectra display absorption features in the visible region, characteristic for the MLCT transition of the grafted ruthenium polypyridyl photosensitizers, as shown in Figure 2 for NiO|RuP4-dppz. As previously reported,52,75,81 surface concentrations were estimated using the following equation (assuming that the molar absorption coefficients ε of the dyes are not modified upon hydrolysis and grafting64): surf. concn (mol ·cm−2) =

Absmax 1000εmax (M−1· cm−1)

(1)

Surface concentrations of 16.1 ± 3.5 and 13.7 ± 0.8 nmol· cm−2 (average out of eight samples) were estimated for RuP4OH-bpy and RuP4OH-dppz, respectively, which is roughly twice more than RuP2OH-bpy (8.7 ± 2.3 nmol·cm−2); this increased grafting efficiency can be directly correlated to the presence of four anchoring groups on the former photosensitizers. Surface concentration determination for related ruthenium tris diimine sensitized NiO films is only scarcely reported in the literature. We previously reported the grafting of RuP2OH-bpy onto PS-b-P2PV-templated NiO films with a surface coverage of 1.5−2.8 nmol·cm−2.52 Using the same photosensitizer, Odobel and co-workers calculated a maximum surface coverage of 1.2 μmol·m−2 (equivalent to 0.12 nmol· cm−2) from Langmuir isotherm plots.38 Finally, a maximum surface loading in the range of 30 nmol·cm−2 was obtained by E


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Figure 3. Schematic principle for electron transfer processes taking place after irradiation of dye-sensitized electrode in the presence of irreversible electron acceptor (IEA) (A). Cathodic photocurrent densities recorded on NiO|RuP2-bpy (B), NiO|RuP4-bpy (C), and NiO|RuP4-dppz (D) electrodes, in the presence of [Co(NH3)5Cl]Cl2 (20 mM) as IEA. The measurements were carried out under chopped light irradiation, either in acetate buffer 0.1 M, pH 4.5 (red), or in phosphate buffer 0.1 M, pH 7.0 (blue), at an applied potential of 0 V vs Ag/AgCl.

light irradiation of the dye-sensitized NiO electrodes, cathodic photocurrents build up (Figure 3), ascribed to the establishment of photoinduced electron transfers from the NiO valence band to IEA, mediated by the excited state of the photosensitizer (Figure 3A). For each dye-sensitized electrode, the measurements were carried out first in acetate buffer (pH 4.5), and then in phosphate buffer (pH 7), under chopped light irradiation (visible light; 50 mW·cm−2). Higher photocurrent densities were, in the three cases, recorded at pH 7, although the difference is faint for NiO|RuP4-dppz: macroscopic photocurrents as high as 170 μA·cm−2 (pH 4.5) and 190 μA·cm−2 (pH 7) were indeed obtained, in the same range as those we previously described with a push−pull organic dye.52 In the absence of IEA in solution, small cathodic photocurrents were recorded (≈35 μA·cm−2 for NiO|RuP4-dppz, see Figure S11 in the Supporting Information), as previously observed52 and tentatively attributed to the reduction of residual traces of oxygen trapped within the nanostructured surface of the dyesensitized electrode.82 Furthermore, nonsensitized NiO electrodes do not display any photocurrent in the presence of 20 mM IEA (at either pH 4.5 or pH 7, Figure S12 in the Supporting

Wu and co-workers for cyclometalated ruthenium sensitizers bearing two carboxylate anchoring groups.42 It is important to highlight that the amount of dye loading is strongly dependent on the NiO film preparation,36 on its thickness, and on the nature of the anchoring groups,38 which prevents any straightforward comparison. Photoelectrochemical Properties of Dye-Sensitized NiO Films. Most of the studies dealing with the grafting of Ru complexes onto NiO assess their photovoltaic performances in acetonitrile,38,40−42 and are thus of limited interest for water splitting applications. Here, the photoelectrochemical properties of the dye-sensitized NiO films were assessed by chronoamperometric measurements in fully aqueous medium, applying a potential of 0 V vs Ag/AgCl in the presence of 20 mM [CoIII(NH3)5Cl]Cl2, used as an irreversible electron acceptor (IEA).52,75 Upon reduction, this complex irreversibly decomposes into [CoII(H2O)6]2+, thus limiting recombination in the electrode diffusion layer. The Gibbs free energies were determined for both hole injection from the excited dye into the NiO valence band (ΔGinj) and electron transfer from the reduced dye to the IEA (i.e. dye regeneration; ΔGreg); these two processes are exergonic for the three dyes (Table 1), which is favorable for photocurrent generation. Indeed, upon visible F


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catalysts.52,83−86 This last result is particularly interesting in the context of DS-PEC applications. Time-Resolved Absorption and Emission Spectroscopies. Ultrafast transient absorption and time-resolved emission measurements were carried out to elucidate the hole injection and recombination dynamics of the series of ruthenium complexes on NiO films. These photoinduced elementary processes are mechanistically essential for photocurrent generation in a photoelectrochemical device. To aid the discussion of the data obtained for the sensitized NiO films, transient absorption of the complexes were recorded first in acetonitrile solution with excitation at 480 nm (Figure S13 in the Supporting Information). The data recorded are in agreement with literature reports on the parent complexes,87,88 which do not carry any methyl phosphonate groups, again revealing that introduction of the anchoring groups does not significantly affect the chromophoric properties: the data for RuP2OEt-bpy and RuP4OEt-bpy exhibit a broad and structureless excited-state absorption (ESA), without any ground-state bleaching (GSB) within the experimentally accessible probe window. This structureless ESA can be assigned to the absorption of the 3MLCT excited state, attributed to ligandto-metal (bpy-π → metal-dπ) charge transfers.89 Interestingly, 95% of the initial ESA signal remains within the experimental time window (∼1.8 ns) for both complexes (Figure S14 in the Supporting Information). This is indicative of the population of a long-lived 3MLCT excited state, typical for Ru tris-bipyridine complexes. The transient absorption spectrum of RuP4OEt-dppz reveals different spectral features compared to RuP2OEt-bpy and RuP4OEt-bpy. Indeed, GSB is observed at 500−520 nm and is progressively blue-shifted over increasing delay times. A broad ESA, peaking at 580 nm, can also be identified. This absorption band increases in intensity over the first 100 ps after photoexcitation and subsequently decays by approximately 20%. A long-lived 3MLCT excited state is also found in RuP4OEt-dppz, as previously observed for other dppz-containing Ru complexes.57,90 Transient absorption data obtained for the complexes grafted on NiO indicate electronic interaction between the complexes and the surface of NiO (see Figure S15 for raw data). Figure 4a,c,e displays the transient absorption spectra of NiO|RuP2bpy, NiO|RuP4-bpy, and NiO|RuP4-dppz photoelectrodes upon excitation at 480 nm; the corresponding kinetic traces at selected probe wavelengths are shown in Figure 4b,d,f. The spectra are characterized by a GSB below 550 nm and broad positive absorption features at higher wavelengths. It can be noted that the point of zero differential absorption (ΔOD = 0) of the immobilized complexes is shifted to longer probe wavelengths compared to the isolated complexes in solution. With increasing time delay, the zero absorption difference is dynamically blue-shifted and the ground state bleach at 500 nm is almost completely recovered within the accessible temporal window. This feature indicates that both relaxation of the excited state and interfacial charge transfer take place.44 The broad positive absorption difference around 660 nm is associated with the π−π* absorption of bipyridine radical anion (bpy•−), as also obtained from electrochemically reduced ruthenium−bipyridine complexes.40,43,91 Accordingly, the decay of positive absorption difference at 660 nm synchronized with the recovery of GSB at 550 nm can be ascribed to the formation of charge separated states as a result of hole injection from excited dye into NiO.41,49 This hole injection forms a charge separated state, which is an indispensable intermediate

Information), confirming that the ruthenium photosensitizers are at the origin of the observed photoelectrochemical activity. In order to evaluate the intrinsic efficiency of each photosensitizer to mediate photoinduced electron transfers, comparison needs to be made by taking into account the amount of grafted dye, i.e. by dividing the photocurrent density (j) by the surface coverage (Γ, estimated by UV/vis absorption measurements). Although displaying a significantly lower driving force ΔGreg (Table 1), RuP4-dppz is the most efficient photosensitizer of the series, with an activity 1.5−2 times higher in acetate buffer, pH 4.5 (12.1 μA·nmol−1·cm−2), than the ones obtained for RuP4-bpy (7.9 μA·nmol−1·cm−2) and RuP2-bpy (5.6 μA·nmol−1·cm−2), respectively (see Table 2). This result Table 2. Cathodic Photocurrent Densities and Stabilities of Photosensitizers at pH 4.5 and pH 7 cathodic photocurrent density (j)a

cathodic photocurrent density per nmol of grafted photosensitizerd

stability (over 10 min) (%)

sensitizer

pH 4.5b

pH 7c

pH 4.5b

pH 7c

pH 4.5b

pH 7c

RuP2-bpy RuP4-bpy RuP4-dppz

−50 −87 −170

−70 −120 −190

5.6 7.9 12.1

7.9 10.9 13.6

80 82 100

90 85 80

a In μA·cm−2, measured on the first irradiation cycle, dark current subtracted; 0.50 cm2 electrode surface. bSodium acetate buffer, 0.1 M. c Potassium phosphate buffer, 0.1 M. dj/Γ in μA·nmol−1·cm−2.

indicates that the specific charge transfer properties of the dppz ligand dominate over other parameters to control photocurrent generation; the electron in the reduced RuP4-dppz is indeed localized on the phenazine moiety, which means at an increased distance from the NiO surface compared to the other reduced dyes. This could make it more accessible for reaction with the electrolyte and also slow down charge recombination, as previously reported for related systems.41 The latter point will be studied and discussed in more detail in the section TimeResolved Absorption and Emission Spectroscopies. Finally, these measurements brought some preliminary information about the stability of the dye-sensitized NiO films under such aqueous working conditions, relevant for DSPEC applications. Apart from the RuP4-dppz sensitized electrode at pH 4.5 (discussed below), a small decrease in the photocurrent density is observed during the first three irradiation cycles, while the photocurrent density then stabilizes for the next cycles. This behavior can be tentatively assigned to some surface reorganization at the beginning of the experiment. No drastic pH effect is observed: 80−90% of the photocurrent density is maintained at pH 4.5 just as at pH 7. By contrast, no loss of activity at all is observed for NiO|RuP4-dppz in acetate buffer pH 4.5, a behavior that we previously observed with a push−pull organic dye.52 The good stability of NiO|RuP4-dppz may be due to a combined effect of a lower water solubility of RuP4-dppz compared to the two other dyes and a lower competition of the acetate buffering species for NiO surface binding. Although a more detailed and systematic analysis of the stability of these dye-sensitized electrodes would be required for a deep understanding of their behavior under photoelectrochemical conditions, RuP4-dppz combines the highest photocurrents of the series with good stability at pH 4.5, the pH of activity of various cobalt-based H2-evolving G


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Figure 4. (left) Transient absorption difference spectra upon excitation at 480 nm at different delay times and (right) kinetic traces at different probe wavelengths of (a, b) NiO|RuP4-bpy, (c, d) NiO|RuP4-bpy, and (e, f) NiO|RuP4-dppz. Insets of (a), (c), and (e) show evolution of absorption difference spectra at around ΔOD = 0 and at isosbestic point, while insets of (b), (d), and (f) show dynamic shift of the probe wavelength at which ΔOD = 0 is observed.

3. The ultrafast component τ1 of ∼200 fs is interpreted as contributions from 1MLCT → 3MLCT intersystem crossing (ISC, typical for this type of complexes), intramolecular vibrational redistribution, andlikelyfast hole injection into NiO (for NiO|RuP4-bpy, see below). The spectral features associated with τ2 = 5.8 ps (NiO|RuP2-bpy) and 19.5 ps (NiO| RuP4-dppz) are qualitatively similar to that found in a related system.44 The negative ΔOD signal at 550 nm, i.e. adjacent to the ground-state bleach toward 550 nm, reflects that hole injection from the excited states of RuP2-bpy and RuP4dppz40,92 to NiO contributes to the observed processes. This is due to the fact that around 530 nm both oxidized Ni centers41,44,93 and reduced RuII polypyridine sensitizers contribute to the differential absorption signal.89 Although the injection rates in NiO|RuP2-bpy and NiO|RuP4-dppz

in obtaining high cathodic photocurrents from the molecularfunctionalized NiO electrodes. Hole injection is further confirmed by time-resolved emission measurements, which are depicted in Figure 5. The data reveals that the emission of the complexes, which is rather long-lived in solution, becomes rapidly quenched on the NiO surface. In agreement with the literature, this finding is associated with photoinduced hole injection from the complex into the NiO.44 To quantitatively analyze the hole injection and recombination kinetics, a triexponential function with an offset reflecting the respective long-lived component was applied to globally fit the transient absorption data. The resulting decay associated spectra (DAS) of NiO|RuP2-bpy, NiO|RuP4-bpy, and NiO| RuP4-dppz are shown in Figure S16 (Supporting Information), and the characteristic time constants are summarized in Table H


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associated spectra, associated with τ3 are rather similar for all ruthenium complexes on NiO. This indicates that the process associated with τ3 stems from charge recombination irrespective of the specif ic molecular structure. During the ultrafast photoinduced dynamics, the intensity of the ESA band integrated between 650 and 700 nm decays by 63, 71, and 43% for NiO| RuP2-bpy, NiO|RuP4-bpy, and NiO|RuP4-dppz, respectively. These numbers are derived based on the integrated ESA intensity recorded at the longest delay times relative to the maximal signal amplitude of the ESA band recorded at 150 fs after photoexcitation. However, it should be noted that the charge recombination associated with τ3 is only partial as a long-lived (on the time window of the experiment) component is observable in the data. These findings are in line with the literature, which reports that in the absence of a redox mediator (as in our measurements) recombination kinetics leading to a decay of the interfacial charge-separated state of NiO(+)−RuIIbpy(−) are characterized with time constants of up to 5 μs.40,41,43 Hence, such slow recombination processes will occur at long-time offsets in our differential absorption data and only the partial subnanosecond recombination kinetics are visible in the experiments performed here. The photophysical model, which summarizes the observations of the ultrafast spectroscopy, is presented in Figure 6. The model is based on the notion that the substitution of the bpy ligands by the anchoring groups does not significantly disturb the chromophoric properties of the RuP2-bpy and RuP4-bpy complexes, compared to [Ru(bpy)3]2+. Thus, upon light absorption the electron density is quasi equally distributed over the three bpy ligands. However, upon fast hole injection, two distinct electronic configurations become possible, i.e. one in which a bpy ligand bearing the phosphonate anchoring groups is reduced and another one in which the unsubstituted bpy ligand is reduced. When the radical anion is formed on a phosphonate-substituted anchoring ligand, relatively fast charge recombination is observed, i.e. the process associated with τ3. On the contrary, if the electron is localized on the nonsubstituted bpy ligand, i.e. more decoupled from the NiO surface, the kinetics of recombination is slowed down, giving rise to the long-lived component observed in our transient absorption data. This shows that, even by as little modifications as asymmetrically substituting a Ru(bpy)3 core with anchoring groups, a molecular push−pull effect can be achieved.44 Discussion of Results from Time-Resolved Spectroscopy in Relation to the Observed Macroscopic Photoelectrochemical Activity. All complexes investigated here to sensitize NiO films reveal sizable photocurrents under the chosen experimental conditions. The magnitude of the photocurrents scale in the following order (see Table 2): NiO|RuP4-dppz > NiO|RuP4-bpy > NiO|RuP2-bpy. This trend does not follow the trend of the rate of hole injection into the NiO, whichcomparing the characteristic time scales for the slowest observable injection time constantis NiO|RuP4-bpy > NiO|RuP2-bpy > NiO|RuP4-dppz. In all the investigated photocathodes, the fastest recombination kinetics appears with a time constant of roughly 400 ps in concert with a slow component (which kinetically extends beyond the accessible time range of our experiment). By contrast, this slowest recombination process results in remaining ESA intensities (integrated in the spectral region between 650 and 700 nm) at long delay times of 37, 29, and 57% for NiO|RuP2bpy, NiO|RuP4-bpy, and NiO|RuP4-dppz of the ESA amplitude right after photoexcitation, respectively. It is thus tempting to

Figure 5. Time-resolved luminescence spectra of (a) NiO|RuP2-bpy, (b) NiO|RuP4-bpy, and (c) NiO|RuP4-dppz. Instrumental responses of time-resolved luminescence measurement are indicated by dashed gray lines.

Table 3. Fitted Time Constants (τ) and Relative Amplitude Decay Measured at Integrated Spectral Range 650−700 nm (A) from Transient Absorption Dataa τ1/ps τ2/ps τ3/ps τ4/ns

(A) (A) (A) (A)

NiO|RuP2-bpy

NiO|RuP4-bpy

NiO|RuP4-dppz

0.3 (0.25) 5.8 (0.13) 422 (0.25) >2 (0.37)

0.3 (0.24) 6.1 (0.17) 361 (0.30) >2 (0.29)

0.2 (0.19) 19.5 (0.07) 400 (0.17) >2 (0.57)

a

The weights of the individual components are derived following a protocol by Wu and co-workers.40,43

estimated here are slower than the rates observed in most organic dye-sensitized NiO electrodes (hundreds of femtoseconds to ∼1 ps),94−96 these values are comparable to those found in other studies related to ruthenium photosensitizers.43,44 Comparing the DAS of the some picosecond components of NiO|RuP2-bpy and NiO|RuP4-dppz to NiO|RuP4-bpy, it becomes apparent that the latter does only reveal a very minor negative ΔOD structure adjacent to the ground-state bleach (see red shift of the 6.1 ps component compared to the long-lived component). This feature is however associated with oxidized Ni centers and reduced RuII sensitizer, i.e. hole injection into the semiconductor. Recalling that cathodic photocurrents were observed for NiO|RuP4-bpy (see Figure 3), it is concluded that in this system dominant parts of the ultrafast hole injection occur beyond the time resolution of the spectroscopic experiment. Apparently increasing the number of anchoring groups increases the likelihood that right upon photoexcitation an electronic state is populated, which is highly prone to hole injection. Along these lines, the 6.1 ps component in NiO|RuP4-bpy might be assigned to some vibrational relaxation occurring after formation of the reduced RuP4-bpy.97,98 τ3 reflects a process in which ground-state bleaching decays without contributions from products of hole injection building up. Hence, τ3 is assigned to charge recombination (vide infra). The magnitude and the spectral contributions, i.e. the decay I


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Figure 6. Photophysical scheme of different recombination pathways on (a) NiO|RuP2-bpy, (b) NiO|RuP4-bpy, and (c) NiO|RuP4-dppz.

nanosecond time scale, and hence it would match the lifetime estimated for the long-lived charge-separated state. Second, photoelectrochemical measurements are carried out at an applied potential of 0 V vs Ag/AgCl. A dependency between the potential applied to the NiO electrode and the charge recombination rate was recently reported by Hammarström and co-workers, from nanosecond time scale measurements made at different applied potentials on NiO films sensitized with a ruthenium tris diimine based dyad.48 According to this study, the NiO band gap states should be almost completely filled with electrons at the applied potential of 0 V vs Ag/AgCl (−0.343 V vs Ag/AgNO3 for comparison with the reported study). With holes rapidly removed from the valence band via the conductive substrate, the reduced dyes formed with our three systems should be greatly stabilized (recombination strongly disfavored); as a consequence, diffusion-controlled reaction with the IEA would be even more favored, in agreement with the photocurrents measured for the three electrodes. This efficient hole collection at the back FTO conductive layer also prevents deleterious NiO dissolution at

correlate the differences in the observed photocurrents with the differences in the recombination behavior of the chargeseparated states. Such long-lived components (>3 ns) have also been previously observed for related ruthenium tris diimine sensitized NiO films,40,43,44 but they represented relatively smaller fractions of the ESA amplitude, for instance 4−13% in the study by Wu and co-workers.40 Conjugated carboxylate anchors were employed in these examples, which are known to strongly modify the electronics of the ligand.44,99 We specifically selected nonconjugated methyl phosphonate functions, and we show in this study that they do not modify the properties of the Ru(bpy)3 chromophore; we believe this could account for the increased weight of this long-lived chargeseparated state. To definitely relate this long-lived charge-separated state to photocurrent generation, we need to also consider its subsequent reaction with the IEA. The electron transfer reaction from the reduced dye anchored at the NiO surface to the irreversible electron acceptor is controlled by diffusion of the IEA in the electrolyte. It thus occursat the fasteston a J



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the electrode−aqueous electrolyte interface, previously observed during extensive cycling at potentials more anodic than 0.7 V vs Ag/AgCl.93,100 Furthermore, when considering the relative amplitudes of the individual kinetic components as obtained from the global fit, it becomes apparent that for NiO|RuP2-bpy and NiO|RuP4-bpy the weights of the processes associated with τ3 and the infinite component amount to roughly 60% (see Table 2), while for NiO|RuP4-dppz these two components account for about 75% of the overall decay. This implies that for the sensitizer bearing the dppz ligand the charge-separated state becomes stabilized, likely due to the interplay of phenazine and phenanthroline based electronic states, which are both accessible in this structure. The specific electronic and geometrical structure of the dppz ligand101,102 allows for excess electron density to be moved away from the anchoring ligands, and hence the weight of the long-lived component is strongly increased compared to the one for NiO|RuP4-bpy, bearing the same number of anchoring groups. This stabilized charge-transfer state in turn leads to much higher photocurrents in the presence of sacrificial electron acceptors, as observed with the RuP4-dppz sensitizer compared to the bpy-based ones.

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Article

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.6b12536. UV−vis absorption spectra, room temperature steadystate and time-resolved emission spectra, transient absorption and decay associated spectra (DAS), cyclic voltammograms recorded in solution for complexes RuP2OEt-bpy, RuP4OEt-bpy, and RuP4OEt-dppz; XPS spectra, positive and negative mode ToF-SIMS spectra, positive mode ToF-SIMS image, UV−vis absorption spectra, transient absorption difference map, decay associated spectra, and chronoamperometric measurements recorded on NiO|RuP2-bpy, NiO|RuP4-bpy, and NiO|RuP4-dppz (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (D.L.). *E-mail: [email protected] (B.D.). *E-mail: [email protected] (M.C.-K.). ORCID

Vincent Artero: 0000-0002-6148-8471 Murielle Chavarot-Kerlidou: 0000-0003-2709-3772

CONCLUSIONS

Author Contributions

The study presented in this paper compares the spectroscopic properties and the photoelectrochemical activities of NiO photocathodes sensitized by ruthenium tris diimine complexes varying by the number of anchoring groups and by the nature of the third ligand. ToF-SIMS was successfully employed to provide mass-related molecular information for the grafted species and to confirm their chemisorption through Ni−O−P bonds. Cathodic photocurrent intensities up to 190 μA·cm−2 were generated in fully aqueous medium upon visible light irradiation in the presence of an irreversible electron acceptor. In addition, femtosecond transient absorption spectroscopy gave access to the kinetic parameters associated with hole injection and charge recombination. The latter is shown to occur over a wide range of time scales, as also recently reported for an organic-dye sensitized NiO electrode.47 Our results establish the following: (i) Increasing the number of anchoring groups from two to four is important to improving the grafting efficiency. (ii) By contrast with the previously reported conjugated carboxylate anchors, substitution of the Ru(bpy) 3 and Ru(bpy) 2 (dppz) cores by two or four methylphosphonate anchors does not modify the electronic properties of the dye; this property is the basis for the photophysical model proposed here. (iii) Additionally, substituting a π-accepting dppz for the bpy ligand stabilizes the charge-separated state, in agreement with the much larger signal remaining on the nanosecond time scale. The higher relative amplitude of the long-lived charge-separated state for NiO|RuP4-dppz, compared to the bpy-based photoelectrodes, provides a rationale for the higher photocurrent intensities. In the future and before their integration into functional water splitting devices, characterization of such dye-sensitized photocathodes by transient absorption studies at different time scalesfrom femtoseconds to microsecondsand with an applied potential will be required for a complete understanding of their performances.

#

N.Q. and R.A.W.: These authors contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the French National Research Agency (PhotoCAT project ANR-14-JTIC-0004-01 and Labex program ARCANE ANR-11-LABX-0003-01), the European Research Council under the European Union’s Seventh Framework Program FP/2007-2013 (ERC Grant Agreement No. 306398), the COST Action CM1202 PERSPECT-H2O and the German Academic Exchange Service (DAAD) for financial support. Colette Lebrun (CEA, INAC−SCIB), M. W. Daniela, and Jean-François Lefebvre (LCBM) are acknowledged for the ESI-MS, the synthetic support, and some fluorescence measurements, respectively.

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